Polymerization catalysts



2,905,645 Patented Sept. 22, 1959 doc 2,905,645 POLYMERIZATION CATALYSTS Arthur William Anderson, Wilmington, John MacMillan Bruce, Jr., Claymont, and Nicholas George Merckling and William Lawrence Truett, Wilmington, Del., assignors to E. I. du Pout de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application August 16, 1954 Serial No. 450,243

5 Claims. 01. 252-429 This invention relates to novel catalyst systems which are highly valuable for the production of solid ethylene polymers and copolymers.

Heretofore, it has been widely known that ethylene can be converted to solid polymers under very high pressures in the presence of catalysts which are capable of yielding free radicals under polymerization conditions.

It has also been known heretofore (US. Patents 2,212,155, 2,475,520, 2,467,234) that certain metal alkyls and Grignard reagents are capable of initiating the conversion of ethylene to solid polymers through a free radical mechanism. Ethylenehas also been converted to solid polymers in the presence of hydrogenation catalysts, particularly in the presence of alkali metals or alkali metal hydrides (British Patent 536,102).

Generally speaking, Friedel-Crafts type catalysts have not been effective for converting ethylene to solid polymers but instead have resulted in the formation of liquid polymers from ethylene; however, it has recently been reported that solid polymers admixed with oils can be obtained by polymerizing ethylene in the presence of aluminum chloride and titanium chloride at elevated temperatures and pressures and advantageously in the presence of HCl-binding metals like aluminum powder (Fischer, German Patent 874,215 Ausgegeben April 20, 1953).

Still more recently, it was disclosed (J .A.C.S. 75,3879) that polymerization of styrene could be made to take place in the presence of a phenyl magnesium bromide-butyl titanate mixture. Attempts to polymerize ethylene at low pressures to solid polymers in the presence of the same mixture (in which the mo] ratio of phenyl magnesium bromide to butyl titanate is 1:1, and which contains no titanium at a valence state of 2.) failed, and it was thus apparent that the prior art mixture of phenyl magnesium bromideand butyl titanate in the form in which it was disclosed, is a different catalyst, and exhibits markedly different properties, as compared. ,with the compositions to be described hereinafter.

Redox systems have frequently been disclosed for poly merization of olefinic compounds. In the past, redox systems have resulted in the formation of highly branched low density polymers, except at extremely high superpressures, at which high density ethylene polymers have been obtained heretofore. In many of these systems a heavy metal compound was employed in combination produced by combining divalent titanium with organic compounds containing ethylenic unsaturation. In specific embodiments, it has been found that titanium compounds having a valence state of two, which may be combined with two radicals (suitable examples being alkoxy radicals,

'alkyl radicals, and radicals which form acids When combined with hydrogen), can be used effectively in the polymerization of ethylene. Said divalent titanium is generally obtained by admixing a titanium compound having a valence state in excess of two with a reducing agent. The quantity of reducing agent which is present must be sufficient to convert the titanium at least in part to a valence state of two. Titanium trichloride is ineffective for converting ethylene to solid polymers. On the other hand, titanium dichloride is an efiective catalyst for ethylene polymerization yielding solid polymers. A test for divalent titanium, which defines the presence or absence thereof, is the ability of the divalent titanium to react with liquid water to form hydrogen. Coordination of the divalent titanium with organic components, etc., does not necessarily destroy its ability as a catalyst nor destroy its ability to produce hydrogen upon reaction with liquid water; in fact, it appears that ethylene is capable of coordinating with the divalent titanium in this manner, and quite possibly this phenomenon has a bearing on the mechanism of the polymerization. There is evidence, as explained hereinafter, that compounds which complex preferentially tend to suppress the polymerization reaction. One group of the catalyst compositions of this invention contain titanium at an average valence below 3, and at least some of the titanium in said catalysts must be at a valence state of two to produce the extraordinary eitects herein reported. The most active polymerization catalyst compositions have all of the titanium at a valence state of two, as measured by the hydrogen evolution method.

.The nature of these coordination complexes is not fully understood, but they are active catalysts or catalyst components which are capable of initiating the polymerization of ethylene in an extremely active manner to produce solid ethylene polymers having relatively little side chain substitution. The density of the polymers obtained through the use of these coordination complexes generally exceeds at least to some extent, the density of polyethylene prepared by the use of free radical types of catalysts except those free radical polymerization processes which employ such extremely high pressures as to produce abnormally high density polyethylene as compared with polyethylene made at moderately high pressure (700 to 1200 atmospheres) by a free radical polymerization process (cf. US. Patent 2,586,833). Furthermore, in particular instances, the organic radical which is combined with a reducing component (cf. US. Patents 2,380,473 7 While various theories have been adin the coordination complex may provide end groups for the solid ethylene polymer. In this connection, a coordination complex prepared from titanium tetrachloride and phenyl magnesium bromide in such proportions as to reduce the average valence of the titanium to below 3 when used as an ethylene polymerization initiator, gives rise to the formation of a solid polymer which appeared, by ultra violet absorption, to contain phenyl groups.

I It is believed that the coordination complexes hereinabove described are novel compounds which have not been employed heretofore in the polymerization of ethylene. By complexing with various components it is possible to control molecular weight of the polymer; e.g. when tri-n butyl amine is the complexing agent, the molecular weight of the polymer is much lower than is obtained under the same conditions when the amine component of the complex is not present. The complexes are difficult to isolate in a pure state, but their presence can be detected from the chemical properties of the mixtures produced when a titanium compound having a valence state abcive 2 is reduced at least in part to a valence state of 2 and admixed with an ingredient which can form a com plex with the titanium in its low state of valence.

So active, as ethylene polymerization catalysts, are the coordination complexes hereinabove described that they can be used for polymerizing ethylene to solid polymers at room temperature and atmospheric pressure. These complexes can also be employed in the manufacture of numerous olefin polymers which heretofore have not been obtainable by any polymerization method whatever.

While the polymerization of ethylene to produce solid polymers in the presence of the catalysts herein disclosed can be carried out iihder extremely mild conditions as stated in the preceding paragraph, it is preferable from aneconomic standpoint to employ moderately high pressures, suitably from 10 to 200 atmospheres or higher, in order to facilitate the handling of ethylene. Much higher pressures, up to several thousand atmospheres, can be employed, but it is not economically desirable to do this in view of the extraordinary activity of the catalysts at lower pressures. Similarly, extremely low temperatures may be employed. The preferred temperatures, however, are within the range of about to 300 C.

The polymerization of ethylene according to the process of this invention, takes place most satisfactorily when the polymerization mixture if substantially moisture-free and also free of other sources of hydroxyl groups. Since water reacts with the catalyst, as hereinabove explained, the water content of the mixture should be kept at the lowest practicable minimum. As in numerous other ethylene polymerization processes, the polymerization mixture in the process of this invention "is preferably kept free of'oxyg'en since oxygen reacts with the catalyst. In practical operations, the oxygen content should preferably beheld below 20 parts per million. Certain compounds which are known to be polymerizable and which are capable of coordinating with the titanium at a valence state of 2 from complexes which are too stable for optimum results, and accordingly, the presence of these compounds should preferably (although not necessarily) be avoided. In this category are ketones and esters. Hydrocarbon solvents, on the other hand, can be used quite efiectively.

Among the reducing agents which are most effective for reducing the valence of the titanium to an averageof below 3, the following may be mentioned:

(1 'Grignard reagents.

(2) Metal alkyls or aryls and similar organometallic compounds.

(3) Zinc metal and metals above zinc in the electro:

motive series.

(4) Metal hydrides.

In specific embodiments, the polymerization mixtures especially those employing inert solvents, such as hydrocarbons, are'homogeneous and contain the active 'coordi nation complex in a dissolved'form. These homogeneous catalyst systems have certain advantages over heterogeneous catalyst systems. In the homogeneous systems, the polymerization takes place very readily in the presence 'of a relatively small amount of the coordination complex. In contrast with this, a somewhat larger quantity or catalyst is necessary if a heterogeneous system'is employed especially if the effective surface area of the catalyst is not extremely large. Good results are obtained when the catalyst is colloidally dispersed. Attempts to employ heterogeneous systems in which the surface area of the catalyst is relatively small, 'have given rise to poorer results. I

In contrast With the foregoing, we have observed that reduction of titanium dioxide to titanium monoxide did not produce an eifective catalyst since the product 'thus obtained was in a non reactive-or refractory stateand did'not form complexes'of the'typ'e'required for 'poly- Example l'i Polymerizati'oh of ethylene using a dry solid catalyst Titanium tetrachloride (4 grams, 0.02 mole) was dissolved in 200 ml. of cyclohexane and 26 cc. of a 3 M ethereal solution of phenyl magnesium bromide (0.08 mole) was added rapidly. The mixture was shaken vigorously for 10 minutes, filtered under nitrogen, and the solid dried at room temperature (l-.0 mm.) to yield 17 grams of a black powder which was pyrophoric.

A mixture of 6 grams of this solid in 100 ml. of cyclehexane was introduced into a 325 ml. shaker tube, the

tube pressured to 500 psi. of ethylene, and the mixture shaken at roomtemperature'for 2 hours. The resulting solid polymer was washed in a Waring Blendor with methanol and hydrochloric acid inmethan'ol, dried overnight in'an air oven at 70 C. Yield 107 grams, inherent viscosity 5.4 ('decahydronaphthalene). 'A film pressed at 200, 20,000 p.s-.i. for 3 minutes was tough and stiffer than commercial polyethylene.

Exempt e I I.i0lymerizati0n of ethylene using a soluble catalyst A solution of 5.6 grams (0.01 mole) of tetra(2-ethyl hexyl)-titanate and 200 ml. of cyclohexane was heated to 50-55? C., and the 15 ml. of a 3 M ethereal solution of phenyl magnesium bromide (0.04 mole) was added rapidly. The mixture was shaken for several ini-nutes and a dark brown solution resulted. There wasno precipitate.

This solution was introduced into a 325 '-ml. shaker tube. The tube pressured to 500 psi. of ethylene,-and the mixture was shaken at 30 C. for -2 hours. The 're' sulting solid product Was washed in a Waring Blendor with successive portions of methanol, hydrochloric acid inmethanol, and acetone, and dried overnight in a 70C. air oven, yielding 16 grams of polyethylene. A film was pressed at 200 6., 20,000 p.s.-i. for 3 minutes. The resulting polymer was tough and stiffer than commercial polyethylene.

Soluble active catalysts also were-prepared from titanium tetrachloride and phenyl magnesium bromide in the followingsolvents: -furan, chlorobenzene, "and n-butyl ether.

Example IIIF POZyIne riZdtiOn of ethylene 'a't'aimosphric To 13.5 (cc. of a 3 M ethereal solution of ethylmagnesium bromide (0.04 mole) in 200 ml. of cyclohexane was added grams (0.02 mole) of titanium tetrachloride. The mixture was shaken vigorously andthen a stream of ethylene was bubbled through it -for 0.4 hour. The mixture was diluted with'methanol, filtered, and the solid washed :Wllh methanol, hydrochloric acid in methanol, and acetone. The resulting solid-polymer was dried under high vacuum at 50 C. A film pressed at--200, 20,000'p.s,i. for 3 minutes was very tough, andhad a density of 0.94.

Example IV.C'0'pblym e'rization of-ethylene with propylene Tire feacti'o'npro'diict of 2 gr ams (dormers er titanium tetrachloride and 13 rnllof a 3M ethereal solution bfphenyl niagfiesiumhfdmide' (0.04 nine in 200 ml. of

s asms Eyclohexane was introduced into a 325 ml. shakertube,

100 grams of propylene added, and the tube pressured to 500 p.s.i. of ethylene. The mixture was shaken at 30 C. for 2 hours, filtered, and washed and dried as previously described, yielding 12.5 grams of copolymer, having an inherent viscosity of 5.4 (decahydronaphthalene). A film pressed at 200 C., 20,000 p.s.i. for 3 minutes had a density of 0.91 (cf. US. Patent 2,396,677), and was qualitatively tougher and more transparent than polyethylene prepared under the same conditions. An infrared determination of methyl groups showed the presence of 3CH /100C.

By decreasing the amount of propylene introduced into the reaction it was shown to be possible to decrease the value of CH;,/ 1000 and increase the density. Thus 50 grams of propylene gave a copolymer having a density of 0.92, and a methyl content of 2CH /100C. Repeating the experiment again with 25 grams of propylene gave a copolymer having a density of 0.93 and a methyl content of 0.7CH /100C.

Example V.Copolymerizatin of ethylene with batadiene A mixture of 3 grams dry solid catalyst (prepared as described in Example I) and 100 ml. of cyclohexane was introduced into a 325 ml. shaker tube. Butadiene (25 grams) was added, and the mixture was pressured to 500 p.s.i. of ethylene. The tube was shaken at room temperature for 2 hours. The product filtered, washed and dried. The yield of copolymer having an inherent Example VI Ethylene was polymerized at a temperature of 100 C. and a pressure of 1000 p.s.i. for 1 hour in the presence. of a mixture which was prepared by adding 26 cc. of an ether solution containing 0.04 mole phenyl lithium to 175 cc. of a solution of 0.02 mole titanium tetrachloride in 175 cc. toluene. The product was washed with an acetone-hydrochloric acid mixture then with acetone and was finally dried at 60 C. in a vacuum to give 5.0 grams of solid ethylene polymer having a density of 0.95.

Example VII Ethylene was polymerized at a temperature of 100 C. and a pressure of 1000 p.s.i. for 1 hour in the presence of a mixture which was prepared by adding 27 cc. of an ether solution containing 0.04 mole phenyl lithium to a suspension of 0.02 mole titanium tetrafluoride in 175 cc. toluene. 0.9 gram of ethylene polymer having a density of 0.95 were recovered after washing and drying the polymer as described in Example VI.

Example VIII A mixture consisting of 0.04 mole titanium tetrachloride, 0.01 mole lithium aluminum hydride (LiAlH 175 cc. toluene and ethylene under a pressure of 1500 J- p.s.i. was heated at 150 C. for 1 hour. After Washing and drying the resulting solid product as described in Example VI, it yielded 8.5 grams polyethylene having a density of 0.97.

Example IX A mixture of 1.5 grams tetrapropyl titanate and 0.03 mole ethyl magnesium bromide in ether was subjected to treatment with ethylene in n-heptane solvent at 200 C. under a pressure of 2500 p.s.i. for 2.5 hours. 1.2 grams of solid ethylene polymer having a density of 0.94 and heated with ethylene at 200 an inherent viscosity (decahydronapnthalene) of 0.73

were obtained.

Example X Example XI A solution of 1 gram hydroxy titanium oleate and 0.03 mole ethyl magnesium bromide in cyclohexane was C. under a pressure of 2500 p.s.i. for 1.5 hours. 1.1 grams of solid polymer contaminated to some extent with oily material was obtained from the resulting product.

Example XII I A solution of 2 grams of octylene glycol titanate and 0.03 mole ethyl magnesium bromide-ether in cyclohexane was heated at C. for 1.5 hours under a pressure of 2500 p.s.i. The resulting product yielding 3.9 grams of polyethylene having a density of 0.95.

Example XIII A solution of 2 grams of triethanol amine titanate and 0.015 mole ethyl magnesium bromide-ether in cyclohexane was heated at 105 C. for 1.5 hours with ethylene at 2500 p.s.i. The resulting product yielded 1.1 grams of solid polyethylene having a density of 0.95.

Example XIV Into a reaction vessel was placed 10 ml. of a 3 molar solution of ethyl magnesium bromide in diethyl ether, 7 grams of titanium trichloride, and 100 ml. of n-hexane. The vessel was evacuated and flushed with nitrogen three times, pressured to 500 p.s.i. with ethylene and heated for 2.1 hours at 93 to C., maximum pressure being 2500 p.s.i. Ethylene was injected periodically during the run to keep the pressure above 1400 p.s.i. during nearly all of the polymerization period. The mixture thus obtained was withdrawn, and polymer was separated by washing with methanol-HCl, methanol-NaOI-I and methanol. The polymer weighed 105 grams and was so high in molecular weight as to make viscosity determination in decahydronaphthalene extremely difiicult.

Example XV To obtain a specimen of titanium dichloride about 50 grams TiCl was dropped into a hot quartz tube (875 C.) during a one-hour period in an atmosphere of hydro gen. The tube, which had an inside diameter of about 2 cm. became plugged at this time. About 10 grams of violet-black solid was collected in a receiver at the end of the tube, the receiver contents being blanketed in hydrogen. The black-purple solid (weight 8 grams) was found to generate hydrogen when dropped into water. This was titanium dichloride. Part of this (2.7 grams) was admixed with 100 ml. cyclohexane, and used as a catalyst for ethylene polymerization in a shaker tube of 330 ml. capacity, for one hour at 197 C., under a pressure of 1000 p.s.i. The yield of solid polyethylene thus obtained was about 1.5 grams.

Example XVI V A solution of 1.4 grams of cadmium dimethyl in about 10 ml. n-heptane was diluted with 40 cc. xylene and 75 cc. of a xylene solution containing 4 grams TiCl The resulting mixture was placed in a shaker tube and subjected to an ethylene pressure of 500 p.s.i. The mixture thereupon was heated for 2 hours at 50 to 74 C. under an ethylene pressure of 500 to 740 p.s.i. The reaction product was washed with methanol and acetone, to yield 0.75 gram of solid polyethylene.

7 Example VII 2.3 grams T101 and 0.86 gram of Al(CH) in 27 'ml.

cyclohexane (injected portionwis'e) gave a product which when washed with cyclohe'xane and acetone yielded 46 grams 'of polyethylene-having a melt index of 1.7.

Example XIX Polymerization of ethylene at 139 to 155 C. for 1 hour at 6000 p.s.i. in the presence of a solution of 0.57 grain of TiCL; and -1-.'5 grams of LiAlQn-hexyl), in 450 ml. cyclohexanegave a product which, when washed with cyclohexane and acetone yielded '50 grams or polyethylene, which has a molecular weight which was too high for determination ofmelt index.

It is to be observed that the foregoing examples are illustrative only and that numerous embodiments of the invention will occur to those who-are skilled in the art.

As hereinabove indicated, the'reducing'component of the polymerization mixture can be varied rather widely, but it is essential'that th'e'redueing component be a sufficiently strong reducing agent and also that it be employed in sufficient quantity to reduce the valence of the titanium, at least in part, to 2.

The products obtained by'polymerizing ethylene with catalysts hereinabove disclosed are solid polymers exclusivelyand are not'contaminated with Friedel-Cratts type of oily polymers.

The activity of the catalyst depends in part upon the nature of the groups'which are attached't'o the titanium atom. It is quite possible that this effect depends upon the Varying degrees ofshielding aroundthe cation, i.e. the shielding powenof the .group attached to titanium influences the activity of the catalyst by infiuencing'the tendency of the titanium to coordinate. Electrical eifects may also play a part in this. 9n the other hand, large organic groups maybe attached to the titanium with beneficial results whensuch groups impart solubility to the catalyst.

The quantity of catalyst employed can be varied over a rather wide range. It is desirable to employ a quantity of catalyst which is'at least largeenough to produce a reasonable rapid ratefora reasonably long period of time. Suitably, the preferred quantity is within the range of 0.1 to 10% based on the weight of'Ti per unit weight monomer.

The polymers which'are made under theconditions hereinabove described frequently have such tremendously high molecular weights that removal of catalyst by dissolving and filtering is extremely diflicult. The best procedurefor obtaining the polymer in a clean form is to wash with acetone-hydrochloric mixture in a Waring Blendor several times followed by washing with acetone and thereafter, if'necess'ary, followed by several acetoneaqueous sodium hydroxide washes and finally by acetonewater wash. Finally, the polymer can be washed with acetone. The products thus obtained are generally snowwhite. 'While'this procedure is highly satisfactory for preparing clean polymer, it is to'be' understood that simpler procedures, such as treatment with water at ele- 8 vated temperatures, willbe entirely suitable for various practica1 applications. For other ,practical applications it is not essential toremove "traces of catalyst.

The structure of the polyethylene made in accordance with .the .process of this invention evidently is charac terizcdby being a-st'raig'ht chain hydrocarbon, with vinyl groups at one or both ends of at least some of the mole.

cules. The infrared measurements indicate very Ilittle methyl substitution and a very small number of vinylidene groups with little or no trans-unsaturation or car bonyl groups.

The ethylene polymers obtained in accordance with the process of this invention are highly valuble in numerous applications especially in the form of films, molded articles, extruded insulation on wire, etc. In those embodiments in which the catalyst is not removed from the polymeric product-or is only incom-. pletely removed, the products are thermally stable, some-. what surprisingly. When thepolymerization is carried out in a system in which the catalyst is dissolved in the inert medium (e.g. when the titanate ester contains octyl groupsorother similar groups=or when'it contains methyl groups but the reducing agent contains phenyl, octyl oroth'er similar group which can-interchange with methyl) the polymerprecipitates from the polymerization mixture in a form which may contain measurable amounts oftitanium eg. as much as 0.5%. Such compositions are highly useful despite their content ot titanium.

It is recognized, however, that the divalent titanium is capable of forming complexes as-above described. It is also recognized that alkyl and aryl, or other hydrocarbon groups, can, by metathetical reactions, become attached to the titanium atom by primary valence-bonds in either the divalent-or trivalent state. Alternatively, such hydrocarbon groups can be initially attached to the titanium, prior to the reduction.

What is claimed is the following:

1. A composition of matter suitable for use in the polymerization of ethylenically unsaturated compounds comprising a substantially moisture-free inert liquid hydrocarbonmedium and-a polymerization catalyst consisting essentially of themixture obtained by treating, in solution in said medium, a titanium tetrahalide in which the halogen'has arr-atomic weightnot'in excess of the atomic weight of chlorine,with a reducing agent of the class consisting of lithium phenyl, LiAl(R) compounds wherein R is a hydrocarbon radical, and-metal alkyls wherein said metal is a member of the class consisting of tin and cadmium, the quantity of said reducing agent being suflicient to lower the valence state of the titanium, at least in part, to below 3.

2. The composition of claim 1 wherein the reducing agent is phenyl lithium.

'3. The composition ofclaim l-wherein the reducing agent is tin tetrabutyl.

4. Thecomposition of-claim 1 wherein thereducing agent is lithium aluminum tetra n-hexyl.

5. The composition of claim 1 wherein the reducing agent is cadmium dimethyl.

References Cited in the-fileof this patent UNITED STATES PATENTS Reid Aug. 15, 1944 Roedel July 5, 1949 OTHER REFERENCES UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,905,645 I' September 22, 1959 Arthur William Anderson et al.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 39, for "from" read form column '7, line 24, for "which has" read which had line 53, for "reasonable" read reasonably Signed and sealed this 15th day of March 1960.,

SEAL) t'test:

KARL H. AXLINE ROBERT C. WATSON Attesting Officer Commissioner of Patents 

1. A COMPOSITION OF MATTER SUITABLE FOR USE IN THE POLYMERIZATION OF ETHYLENICALLY UNSATURATED COMPOUNDS COMPRISING A SUBSTANTIALLY MOISTURE-FREE INERT LIQUID HYDROCARBON MEDIUM AND A POLYMERIZATION CATALYST CONSISTING ESSENTIALLY OF THE MIXTURE OBTAINED BY TREATING, IN SOLUTION IN SAID MEDIUM, A TITANIUM TETRAHALIDE IN WHICH THE HALOGEN HAS AN ATOMIC WEIGHT NOT IN EXCESS OF THE ATOMIC WEIGHT OF CHLORINE, WITH A REDUCING AGENT OF THE CLASS CONSISTING OF LITHIUM PHENYL, LLAL(R)4 COMPOUNDS WHEREIN R IS A HYDROCARBON RADICAL, AND METAL ALKYLS WHEREIN SAID METAL IS A MEMBER OF THE CLASS CONSISTING OF TIN AND CADMIUM, THE QUANTITY OF SAID REDUCING AGENT BEING SUFFICIENT TO LOWER THE VALENCE STATE OF THE TITANIUM, AT LEAST IN PART, TO BELOW
 3. 